Mordant azo dyestuffs



Patented June 24, 1930 UNITED, STATES PATENT 013F101:

MORDECAI MEN DOZA AND KENNETH IIERBERT SAUNDERS, F MANCHESTER, ENGLAND,

ASSIGNORS TO BRITISH DYESTUFFS CORPORATION LIMITED, 01 MANCHESTER,

ENGLAND No Drawingnl Application filed September 29, 1926, Serial No.

November 13, 1925.

I In a copending application of one of us (Saunders) Ser. N 0. 53,404,filed August 29,

1925, there is described a new class of azo dyestuffs adapted formordant dyeing with- 5 0111; substantial change in shade. These new azodyestufis are mixed diaryl sulphones which are characterized by havingthe chelate group separated from and connected to the chromophoricportion of thedyestufi by a sulphone bridge; the sulphone bridge actingas a chromophoric screen, Hence, when these new dyestuffs are fixedonanimal or.

the grouping represented by R possessing.

chromophoric properties and in which the OH and COOH groups attached tothe R are ortho to each other.

Such azo dyestuffs may be derived from 1 intermediates which are mixeddiaromatic sulphones having the general formula 1 wherein R represents abenzene residue and R represents a benzene or naphthalene res due, bothof which may be further substv tu'ted, a2 isl or 2 and in which the -OHand COOH groups attached to the R are ortho to each other. Theseinterinediat'esare new in themselves and in certain other and c0-pending applications Ser. Nos. 303,371 and 398,805, filed asdivisions-of the acknowledged application Ser. No. 53,404, intermediatesof this general class are set forth-and claimed Application Ser. No.303,371 specifically relates to the diamine diaryl sulphones of thegeneral class indicated above. In the acknowledged application Ser. No.

53,404 methods of produclng the new inter-- mediates are also disclosed.Mixed amino such mozemuv'r Azo nvnsrurr's 138,567, and in Great Britaindiaryl sulphones are produced byvcon densing ortho hydroxy-carboxy arylsulphinic acids with aromatic nitro compounds containing a labilehalogen atom, and then reducing the nitro diaryl sulphone so produced-toform the amino diaryl sulphone. Sulphino salicylic acid, itshomologues,(such as sulphino ortho or para cresotinicacid) or substitution products(such as'sulphino'halogeno salicylic acids) may be 'used. Mono anddinitrochlorbenzenes may be used, for instance 2:4-dinitrochlorbenzene,i

' Said copendingapplication Sen No. 53,404

is specifically directed to azo dyestuffs derived from the" mono aminodiaryl sulphones,

and the diamino diaryl sulphones inwhich one of the amino sulphonesbeing the fir'stcom- .Our' present invention relates to 1 furtherdevelopments in the'production of azo dyestufis adapted to mordant 5dyeing without substantial change in shade when fixed on the fiber, andit relatesto acertain class of azo dyestuffs of this general character.This'certain class of azo dyestuffs may be represented by thegeneral'formula 'H'OO'C 3 Rr-sor-R HO l wherein R represents a benzeneresidue'and amino groups has been acylated,

R represents a benzene or-naphthalene residue having an azo groupattached thereto, the group represented by 7 R possessing chromophoricproperties and in'which the OH and' COOI-I groups attached to the R areortho to each other. Such azo dyestufls may be 'derived from-the generalclass of diamino diaryl sulphones claimed in Ser. No. 303,371. Thesediamino diaryl sulphones may be represented by the general formulawherein R represents a benzene residue and R represents a benzene ornaphthalene residue, both of which may be further substituted, and inwhich the OH and -COOH with increasing complexity deepen in shade fromyellow and brown towards the blue end of the spectrum. Mono and polyazodyestuffs may be produced. The finished dyestufi molecule may contain amolecule of one or more of the same or difierent diamino sulphones. Anyof the methods known to dye.- stufi technology may be employed inbuilding upxthe new dyestuffs including for example the formation ofdyes of the Bismarck brown type by the action of nitrous acid uponexcess of a diamino sulphone ofthe nature described.

The following compounds are examples of the general class of diaminecompounds disclosed in acknowledged copending application Ser. No.53,404 and which may be used duce a disazo dye. Suchdisazo dyes may berepresented by the general formula in our invention.

Hooc NH:

H0 so M Nn, (I)

HOQSOFONHI (II) Hal .v

H000 NHm H0 soC-nm (In) We have found that diamines of the general classto which the above diamines belong couple readily with-diazo compounds,including in this term, diazotized monoamino compounds and. tetrazotizeddiamino compounds which are suitable as azo dye components. Monoazo dyesare produced when diazotized monoamino compounds are coupled with thediamine. These monoazo dyels may be represented by the general formu awherein R represents a benzene residue and R represents a benzene ornaphthalene residue, both of which may be further substituted, and Rrepresents a coupled azo dye component from a diazo compound and inwhich the COOH and -OH groups at tached to'the R are ortho to eachother. Disazo dyestuffs are produced when tetrarepresent both the monoN=NR wherein R and B monoazo dyes.

zotized diamino compounds are coupled with the diamino diaryl sulphone.These disazo dyes may be represented by the general forother methods.The monoazo dyes produced given further as indicated above may 'betreatment to convert them into disazo dyes. For instance the diazotizedmonoamino compound may contain a nitro group which after coupling withthe diamino sulphone may be reduced and diazotized and coupled with asuitable azo dye coupling compgnent to prowherein R represents a benzeneresidue and R represents a benzeneor naphthalene residue, both of whichmay be further substituted, and R and R represent coupled residues ofazo dye components.

A generic formula which can be used to and the disazo dyes of ourinventionis:

Rr-S0r-ih-Y I H0 I wherein R and R have theirp'revious significance andY represents a. ,substituent group such as -N=N-R or *N';=NR are coupledresidues of azo dye components. 7

Under the present invention monoazo and ,disazo dyes of various typesmay 'be produced, all of which-have-a characteristic structuralarrangement which permits their use in mordant dyeing withoutsubstantial change in shade when fixed on the fiber. The

present application is specifically directed to Our copendingapplication Ser. No. 303,366 which is a division of the presentapplication, is specifically directed to the disazo dyes. We have hereindisclosed the broad scope of our invention and the following examplesare given as specific illustrations of the broad invention and theseexamples in no way limit the scope of'the invention. The parts are givenby weight.

' Ea wmple I 17.3 parts of sulphanilic acid are dissolved coon s05 on NHI parts of the diamino sulphone I, dissolved in .500 parts of water andparts of soda ash at 510 C. Coupling is rapid and when complete thedyestuif is salted out, filtered ofi and' dried. v

The new dyestuif is an orange powder, having the probable constitution:

. I NZN SOz- COOH SOaH NH -NH:

Wool is dyed golden orange from an acid bath, becoming greener on'after-chroming, whereupon the dyeing becomes fast to milling and itskindred processes. Printed on cotton with.a chrome mordant it yieldsgolden orange shades fast to warm soap.

Working in the same manner as above, and with equivalent quantities,metanilic acid yields a dyestufi' of a slightly greener shade,naphthionic acid a bright orange and p nitraniline-o-sulphonic acid ayellowish-red,

all the prints being fast to warm soap when applied to cotton with achrome mor dant.

Example I I 21.8 parts of p-nitraniline-o-snlphonic acid aredissolved'in 500 parts of water with 5.6 parts of soda ash. The solutionafter cooling is run slowly into 2515 parts of a solution ofhydrochloric acid (36 per cent) diluted with 250 parts of water;Diazotization is carried out at 0*5 C. by 6.9 parts of sodium nitritedissolved in 50 parts of water. When diazotization is complete the diazocompound is run down with stirringintoa solution of 30.8

parts of diamino-sulphone I, dissolved in 550 parts of water with 56parts of sodium bicarbonate at 510 C.

After about one hour there is added a solution of 50 parts ofcrystallized sodium sulphide in 50 parts of water. Reduction proceedswith rise of temperatureto 1520 C.

and this'is maintained for a further four hours. The solution is thenrendered neutral with hydrochloric acid followed by a further additionof 25.5 parts of the 36 per cent s0ll1- tion of hydrochloric acid. Thesecond diaz0 tization is carried out at 0-5 C. with 6.9 parts of sodiumnitrite dissolved in 50 parts of water. The new diazo compound is thenrun into a solution. of 30.8 parts .of the diaminosulphone I, and. 35parts of soda ash in 500 parts of waterat 5-10" G.-

The dyestufl' is salted out after some hours stirring. It formswhen drya dark reddishbrown powder, which has the probable constitution: v

N:N NB NB, OH

"NH, L NL-N, so coon Wool is dyed dark orange from an acid bathbecoming, browner on chroming and at the same time fast to milling andso forth. Printed on cotton cloth with a chrome mordant there isobtaineda reddish-brown shade fast to warm soap; i i

Ema. III

34.4 parts of benzidine-m-dis'ulphonic acid are dissolved in 500 partsof water with 11 parts of soda ash and after cooling the solution is rundown with stirring into 51 parts of a 36- per cent solution ofhydrochloric acid. Diazotization is carried out at 5 C. with 13.8 partsof sodium nitrite in 100 parts of water.

The tetrazo compound is then run down slowly with stirring into asolution of 61.6 parts of the diamino-sulphone I, in 1000 parts of waterand parts of soda ash at 510 C. The dyestufl' is salted out whencombination is complete as shown by the usual tests. It has the probableconstitution;

N:N so coon NHz- N11,; on

NH; NH, on

N:-N so?" 00011 When dry the new dyestuif forms a yellow powder. Wool isdyed deep golden yellow from an acid bath, becoming dull gold onchroming. With a chrome mord'ant cotton is printed in brightyellow-orange shades fast to warm soap,

What we claim and desire to secure by L tters Patent .is v

1 In the manufacture of azo dyes, the

process which comprises coupling a compound containing a diazo groupwith a diaminodiaromatic sulphone having the probable formula coonNHIO-SO|-R I on NH: wherein R represents a benzeneresidue and in whichthe hydroxyl and carboxyl groups are ortho' to. each other.

2. As new d e materials, products having in the form of ree acid theformula N=NR| NHj -form of free acid the formula NH so on in which R'represent's an aromatic radical,

not itself containing'an azo group, the said products being soluble inalkali to colored solutions.

4. As a new dye material the product having in the form of free acid theformula N:N coon N0 NnOsmO I NH:

which is a red powder, giving in water a reddish orange solution.

5. Azo dyes carrying achelate group and I adapted for mordant dyeingwith the chelate group separated from and connected to the chromophoregroup by a sulphone bridge, said azo dyes being mixed sulphones havingthe probable formula adapted for mordant dyeing with the chelate.

group separated from and connected to the chromophore group by asulphone bridge, said azo dyes being mixedsulphones having the probleformula NH: HOOC ln1-s ORN=N-R| no B re resents-a benzene or na hthaleneresi due, 0th of which may be rther substituted, R re'presents' acoupled azo dye component from a diazo compound and in which I the COOHand the OH groups attached to the R are ortho to each other, the saidvdyes producing shades which are substantially unchanged when chromed.

7. Azo dyes carrying a chelate group and adaptedfor mordant dyeing withthe chelate group separated from and connected to the chromophore groupby a sulphone bridge, said azo dyes being mixed sulphones having theprobable formula -unchanged when chromed.

8. Azo dyes carrying a chelate group and adapted for mo'rdant dyeingwith the chelate group separated from and connected to the chromophoregroup by a sulphone bridge, said azo dyes being mixed sulphones havingthe probable formula H000 NH:

the said dyes producing shades which are substantially unchanged whenchromed.

' 9. Monoaz o dyes carrying a chelate group and adapted for mordantdyeing'with the chelate group separated from and connected to thechromophore group by a sulphone bridge, said monoazo dyesbeing mixedsulphones having the probable formula to, the grouping represented by Rpossessing chromophoric properties and in which both R and R maybefurther substituted and the COOH and OH groups attached to the R areortho to each other, and the OH group is para to the sulphone bridge.'10. In the manufacture of azo dyes, the wherein R represents a benzeneresidue and process which comprises coupling a diazo bridge,

compound with a a component having the probable formula wherein Rrepresents an aromatic residue which may be further substituted.

11. As new products, the azo dyes prepared by coupling a diazo compoundwith a component having the probable formula.

, NH: HOOC OSOPii.

I. 11TH: wherein R represents an aromatic residue which may or may notbe further substituted.

12. A20 dyes carrying a chelate group and, adapted for mordantdyeingwith the chelate groupseparated from and connected to theohromophore group by a sulphone said azo dyes being mixed sulphoneshaving the probable formula nooo no NH:-

wherein R represents a benzene residue and R represents a benzene ornaphthalene resi-, due, both of which may be further substituted and inwhich the OH and the COOH groups are ortho to each other, and Yrepresents the substituent group N= R5 N=N R7 wherein R and R arecoupled residues of azo dye components, the said dyestuffs producingshades which are substantially when chromed.

In testimony whereof we have signed our names to this specification.

MORDECAI MENDOZA. KENNETH HERBERT SAUNDERS.

unchanged

